EP0459285A1 - Esters benzyliques d'acides cyclopropane carboxyliques substitués en position ortho - Google Patents

Esters benzyliques d'acides cyclopropane carboxyliques substitués en position ortho Download PDF

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Publication number
EP0459285A1
EP0459285A1 EP91108247A EP91108247A EP0459285A1 EP 0459285 A1 EP0459285 A1 EP 0459285A1 EP 91108247 A EP91108247 A EP 91108247A EP 91108247 A EP91108247 A EP 91108247A EP 0459285 A1 EP0459285 A1 EP 0459285A1
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Prior art keywords
alkyl
phenyl
halogen
ortho
alkenyl
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EP91108247A
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German (de)
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EP0459285B1 (fr
Inventor
Franz Dr. Schuetz
Hubert Dr. Sauter
Norbert Dr. Goetz
Jochen Dr. Wild
Hans-Josef Dr. Wolf
Reinhard Dr. Doetzer
Gisela Dr. Lorenz
Eberhard Dr. Ammermann
Christoph Dr. Kuenast
Uwe Dr. Kardorff
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BASF SE
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BASF SE
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Priority claimed from DE4017488A external-priority patent/DE4017488A1/de
Priority claimed from DE4024094A external-priority patent/DE4024094A1/de
Application filed by BASF SE filed Critical BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the invention also relates to a process for the preparation of these compounds, their use as fungicides and their use for controlling pests, and fungicidal agents and pesticides which contain these compounds as active substances.
  • EP-A 310 954 discloses, inter alia, fungicidally active ortho-substituted benzyl esters of cyclopropanecarboxylic acids of the type of the compounds I whose cyclopropane ring is unsubstituted or carries a methyl, dichlorophenyl radical or a differently substituted phenyl radical. Furthermore, EP-A 354 571 et al. 2- [1- (trifluoromethyl) cyclopropylcarbonyloxymethyl] phenyl and 2- [1- (trimethylsilyl) cyclopropylcarbonyloxymethyl] phenyl-glyoxylic acid methyl ester-0-methyloxime are known. An insecticidal action is not known from the publications mentioned.
  • the invention was based on new ortho-substituted benzyl esters of cyclopropanecarboxylic acids as an object.
  • R is a phenylalkenyl group
  • the E configuration on the double bond is particularly preferred.
  • the isomers can be separated by the customary methods, for example by crystallization or chromatography. Compounds with an E configuration are particularly preferred. The mixtures and the individual isomers are effective and are encompassed by the invention.
  • the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I can be obtained in various ways, preferably by converting a cyclopropanecarboxylic acid II in a manner known per se, in an inert solvent such as ethanol, with a base into the carboxylate anion and using this anion with an ortho-substituted benzyl compound III (cf. Synthesis 1975, 805):
  • L denotes a nucleophilic leaving group, in particular a sulfonyl radical such as methanesulfonyl, trifluoromethylsulfonyl, p-toluenesulfonyl, p-bromophenylsulfonyl or a methyl sulfate radical, particularly preferably a halogen atom such as chlorine, bromine and iodine.
  • a sulfonyl radical such as methanesulfonyl, trifluoromethylsulfonyl, p-toluenesulfonyl, p-bromophenylsulfonyl or a methyl sulfate radical, particularly preferably a halogen atom such as chlorine, bromine and iodine.
  • Alkali metal hydroxides such as sodium and potassium hydroxide and triethylamine are particularly suitable as bases.
  • the reaction of the carboxylate anion with the benzyl compound III is expediently carried out in a solvent or diluent such as acetone, acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide, N-methylpyrrolidone, N, N'-dimethylpropylene urea and pyridine or, using a phase transfer catalyst, in a 2-phase system consisting of water and a hydrocarbon such as carbon tetrachloride.
  • a solvent or diluent such as acetone, acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide, N-methylpyrrolidone, N, N'-dimethylpropylene urea and pyridine
  • a phase transfer catalyst in a 2-phase system consisting of water and a hydrocarbon such as carbon tetrachloride.
  • phase transfer catalysts are e.g. Trioctylpropylammonium chloride and cetyltrimethylammonium chloride (cf. Synthesis 1974, 867).
  • reaction temperature is between 0 ° C and the boiling point of the solvent, preferably between 20 and 130 ° C.
  • cyclopropanecarboxylic acids II are known or can be prepared by processes known per se [see e.g. Synthesis, 738 (1987); Zh. Org. Khim 16: 2086 (1980); J. Am. Chem. Soc. 106: 6642 (1984); Chem. Ber. 116: 3895 (1983); Helv. Chim. Acta 69, 1655 (1986); Chem. Ber. 119: 3694 (1986); Chem. Letters, 475 (1989); J. Organometal. Chem. 46, 73 (1972); Gazz. Chim. Italian 100, 566 (1970); J. Org. Chem. 48, 2472 (1983) and J. Org. Chem. 47, 893 (1982)].
  • the reaction temperature is generally between 20 and 60 0 C.
  • the hydroxymethylene derivative Va can be obtained, for example, by base-catalyzed reaction of methyl 2-methylphenylacetate with methyl formate in an inert solvent such as diethyl ether and tetrahydrofuran, the base being e.g. Sodium hydride can be used (cf. Ann. Chem. 424, 214 (1921)).
  • Ortho-substituted benzyl compounds 111 where X is nitrogen and L is chlorine or bromine, can be obtained in various ways, advantageously by halogenating the methyl 2-methylphenylglyoxylate-O-methyloxime VI.
  • chlorine or bromine can be used in an inert solvent, for example carbon tetrachloride, or halogenating agents such as N-chloro and N-bromosuccinimide [cf. Appl. Chem. 71, 349 (1959)] can be used in CC1. 4
  • halogenating agents such as N-chloro and N-bromosuccinimide [cf. Appl. Chem. 71, 349 (1959)] can be used in CC1. 4
  • elemental chlorine or bromine it is advisable to carry out the reaction photochemically by irradiation with sunlight.
  • the 2-methylphenylglyoxylic acid methyl ester-O-methyloxime VI known from DE-A 36 23 921 is advantageously obtainable from the 2-methylphenylglyoxylic acid methyl ester by reaction with 0-methylhydroxylamine hydrochloride or with hydroxylamine hydrochloride, in which case an oxime is primarily formed, which is then treated with a methylating agent such as methyl chloride, methyl bromide, methyl iodide and dimethyl sulfate.
  • a methylating agent such as methyl chloride, methyl bromide, methyl iodide and dimethyl sulfate.
  • L chlorine or bromine
  • reaction is conveniently carried out in a solvent or diluent, e.g. Dimethylformamide, in the presence of a base, e.g. Potassium carbonate.
  • a solvent or diluent e.g. Dimethylformamide
  • a base e.g. Potassium carbonate.
  • the reaction temperature is generally between 20 and 130 ° C.
  • the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I are suitable as fungicides and for combating pests.
  • the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides.
  • the compounds are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. It is used before or after the infection of the materials, plants or seeds by the fungi.
  • otho-substituted benzyl esters of cyclopropanecarboxylic acids are also suitable for controlling pests from the class of the insects, arachnids and nematodes. They can be used as pesticides in crop protection and in the hygiene, stored product protection and veterinary sectors.
  • the harmful insects include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobisturaumumone, Cheimatobisturaumumone Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Heliothiothisis, Grapholita melliella, Grapholita mellisella , Hibernia
  • Diptera From the order of the two-winged plants (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropucitae, Cordylobia anthropucita, brassylaciaacropucine, Brassylaciaacropacine, Cylobia anthropuca , Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia
  • Thrips for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
  • From the order of the hymenoptera for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • Heteroptera From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratidularis, Parsma viralisea, Pies .
  • bugs Heteroptera
  • Acrosternum hilare Blissus leucopterus
  • Cyrtopeltis notatus Dysdercus cingulatus
  • Dysdercus intermedius Eurygaster integriceps
  • Euchistus impictiventris Leptoglossus phyllopus
  • Lygus lineolaris Lygus pratidularis
  • Parsma viralisea Pies .
  • Orthoptera From the order of the straight-winged wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Peranoplascus sprana, Melanopladus sprana Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
  • Orthoptera for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus
  • arachnids such as Amblyomma americanum, Amglyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, shodelodexi, iodon eroniophyus, Eotetroniiuncus, Iotetranyi odus Ixodes rubicundus, Ornithodorus moubata Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei
  • Amblyomma americanum such as Amblyomm
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetrodera triflolii, stick and leaf wholes, e.g.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application forms depend on the purposes; in any case, they should ensure a fine and uniform distribution of the ortho-substituted benzyl ester of a cyclopropanecarboxylic acid.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomi
  • the active ingredient concentrations in the ready-to-use preparations can be varied over a wide range.
  • the agents contain between 0.0001 and 95, preferably between 0.01 and 90% by weight of active ingredient.
  • Formulations with more than 95% by weight of active ingredient can be applied successfully with the ultra-low-volume process (ULV), and even the active ingredient can be used without additives.
  • UUV ultra-low-volume process
  • the application rates in fungicidal compositions are between 0.02 and 3 kg of active ingredient per ha.
  • the new compounds can also be used in material protection (wood protection), e.g. against Paecilomyces variotii.
  • active compound 0.001 to 50 g, preferably 0.01 to 10 g, per kg of seed are generally required.
  • the application rate of active ingredient for controlling insects is 0.02 to 10, preferably 0.1 to 2.0 kg / ha under field conditions.
  • the agents according to the invention can also be present together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1, if appropriate also only immediately before use (tank mix). When mixed with fungicides or insecticides, the spectrum of action is increased in many cases.
  • agents or the ready-to-use preparations produced therefrom such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.
  • Example 1c Analogously to Example 1c, 24.0 g (0.13 mol) of tert-butyl 1-allyl-cyclopropanecarboxylate (prepared according to Example 1a) were reacted with 14.9 g (0.13 mol) of trifluoroacetic acid. Yield: 90%; colorless oil.
  • Example 3 Analogously to Example 3, 2.3 g (18 mmol) of 1-allyl-cyclopropanecarboxylic acid (prepared according to Example 1c) with 1.1 g (20 mmol) of potassium hydroxide were converted into the potassium salt of 1-allyl-cyclopropanecarboxylic acid and this was converted into 50 ml of dimethylformamide reacted with 4.3 g (15 mmol) of 2- (bromomethyl) -phenyl-glyoxylklareme methyl-O-methyloxime. Yield: 84%; colorless oil.
  • the oily crude product was overlaid with pentane and brought to crystallization by rubbing on the vessel wall. Yield: 64%; M.p .: 58-60 ° C; white crystals.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP91108247A 1990-05-31 1991-05-22 Esters benzyliques d'acides cyclopropane carboxyliques substitués en position ortho Expired - Lifetime EP0459285B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4017488A DE4017488A1 (de) 1990-05-31 1990-05-31 Ortho-substituierte benzylester von cyclopropancarbonsaeuren
DE4017488 1990-05-31
DE4024094A DE4024094A1 (de) 1990-07-30 1990-07-30 Ortho-substituierte benzylester von cyclopropancarbonsaeuren
DE4024094 1990-07-30

Publications (2)

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EP0459285A1 true EP0459285A1 (fr) 1991-12-04
EP0459285B1 EP0459285B1 (fr) 1994-12-14

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EP91108247A Expired - Lifetime EP0459285B1 (fr) 1990-05-31 1991-05-22 Esters benzyliques d'acides cyclopropane carboxyliques substitués en position ortho

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US (1) US5371268A (fr)
EP (1) EP0459285B1 (fr)
JP (1) JP2986246B2 (fr)
KR (1) KR910019965A (fr)
AT (1) ATE115540T1 (fr)
AU (1) AU632421B2 (fr)
CA (1) CA2043090A1 (fr)
DE (1) DE59103850D1 (fr)
DK (1) DK0459285T3 (fr)
ES (1) ES2066264T3 (fr)
HU (1) HU212872B (fr)
IL (1) IL98082A (fr)
NZ (1) NZ238298A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100364483B1 (ko) * 1994-12-20 2003-03-26 킴벌리-클라크 월드와이드, 인크. 신장성,반색조인쇄방법및이로써인쇄된기재

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Publication number Priority date Publication date Assignee Title
US20080188689A1 (en) * 2007-02-06 2008-08-07 Gauri Sankar Lal Preparation of organic compounds bearing a trifluoromethyl group on a quaternary carbon
CN102531898A (zh) * 2011-11-16 2012-07-04 江苏华达化工集团有限公司 对环己酮甲酸酯经氟化生产4,4-二氟环己基甲酸酯的方法
WO2020092802A1 (fr) * 2018-11-01 2020-05-07 The University Of Memphis Research Foundation Contrôle de biofilms avec des acides gras cyclopropanés

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0103957A2 (fr) * 1982-07-26 1984-03-28 National Research Development Corporation Esters benzyliques substitués, leurs intermédiaires, leurs procédés de préparation et utilisation des esters comme pesticides
EP0310954A1 (fr) * 1987-10-07 1989-04-12 BASF Aktiengesellschaft Esters benzyliques orthosubstitués et fongicides contenant ces composés
EP0354571A1 (fr) * 1988-08-12 1990-02-14 BASF Aktiengesellschaft Oxime-éthers, procédé pour leur préparation et fongicides les contenant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE354571C (de) * 1922-06-13 Josef Michael Wenz Unmittelbar beheizter Backofen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0103957A2 (fr) * 1982-07-26 1984-03-28 National Research Development Corporation Esters benzyliques substitués, leurs intermédiaires, leurs procédés de préparation et utilisation des esters comme pesticides
EP0310954A1 (fr) * 1987-10-07 1989-04-12 BASF Aktiengesellschaft Esters benzyliques orthosubstitués et fongicides contenant ces composés
EP0354571A1 (fr) * 1988-08-12 1990-02-14 BASF Aktiengesellschaft Oxime-éthers, procédé pour leur préparation et fongicides les contenant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100364483B1 (ko) * 1994-12-20 2003-03-26 킴벌리-클라크 월드와이드, 인크. 신장성,반색조인쇄방법및이로써인쇄된기재

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AU7801391A (en) 1991-12-05
DE59103850D1 (de) 1995-01-26
HUT57698A (en) 1991-12-30
IL98082A0 (en) 1992-06-21
JP2986246B2 (ja) 1999-12-06
NZ238298A (en) 1994-06-27
ES2066264T3 (es) 1995-03-01
CA2043090A1 (fr) 1991-12-01
ATE115540T1 (de) 1994-12-15
JPH04235945A (ja) 1992-08-25
KR910019965A (ko) 1991-12-19
US5371268A (en) 1994-12-06
AU632421B2 (en) 1992-12-24
DK0459285T3 (da) 1995-01-23
IL98082A (en) 1994-12-29
EP0459285B1 (fr) 1994-12-14
HU212872B (en) 1996-12-30

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